Halogenated aminothionaphthene-z



Patented Oct. 14, 1930 UNITED STATES PATENT? .OFFICE RICHARD HERZ, 0F FRANKFORT-ON-THE-MAIN, FRANZ FARR, OF FECHENHEIM, NEAR v FRANKFORTON-THE-MAIN, AND KARL THIESS AND CARL JOSEF KELLER, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE HALOGENATED AMINOTHIONAPHTHENE2.3-INDOLE-INDIGOID DYESTUFFS No Drawing. Application filed February 4, 1928, Serial No. 252,038, and in Germany February 14, 1927.

Our present invention relates to newvat dyestufl's of the 2-thionaphthene-3-ind0lindigo series and process of preparing them.

We have found that dyestuffs of valuable tinctorial properties are obtained by condensing 6-amino-keto-thionaphthene with a 5.7 -dihalogenisatin and introducing two chlorine atoms into the 5.7 -position of the thionaphthene side, or by condensing 5.7-d1- chlor-6-arnino-keto-thionaphthene with a5]- dihalogenisatin. The dyeings produced by means of these new dyestuffs have over the brown dyestuffs described in U. .S. A. specification No. 968,697 the advantages of a much purer shade and of a better fastness to kierboiling and to light.

new dyestuffs can be obtained by chlorinating the condensation products from 6-an1inov keto-thionaphthene and 5.7 -dihalogenisatins with sulfuryl chloride. It is thus possible to 5 introduce the chlorine uniformly into the 5 and 7 position of the keto-thionaphthene side.

This result could not be expected, since when chlorinating 6-amino-2-thionaphthene 3 indolindigo which has not yet a halogen in the indol residue, heterogeneous dyestuffs are obtained with a bad yield which cannot be used for dyeing purposes.

The chlorination can be carried outwith or without using an indifferent diluent.

5 The 5.7-dichloro-6-amino-ketb thionaphthene can be prepared by treating Q-amino- 4.6 dichloro 5 acetlainino-l-thioglycollic acid according to the process described in German Patents Nos. 184406, 190291, 190674;

0 and 202696 or by treating 4-amino-2.6-di- We have furthermore found that the said course It is then filtered hot, washed first. with glacial acetic acid and afterwards with water until there is a neutral reaction, and dried. 45.2 parts of the condensation product thus obtained are suspended in 500 parts of chlorobenzene and to this suspension are added at 30 C. 30 parts of sulfuryl chloride. The mass is first stirred at 30 C. for two hours, then gradually heated to 70 C., kept at this temperature for 5 to 6 hours, allowed to cool and filtered. The dyestuff thus produced is freed from the chlorobenzene still adhering to it by means of steam and finally dried.

It is a brown powder dissolving in concentrated sulfuric acid to a reddish-violet solution which becomes pure red when allowed to stand for some time. It dyes cotton from a yellow hydrosulfite Vat pure yellow islvbrown tints which are distinguished by their very good fastness to washing'and light.

TIT]

' obtainable according cording to the preceding The dyestuif has the following formula:

uni carbonate, the whole is heated to boiling for 4 to 5 hours. The condensation product which separates is filtered while hot, washed with a small quantity of alcohol and dried.

36.3 parts of the 6-amino-2-thionaphthene- 5.7 dichloro-S-indolindigo thus obtained are suspended in 300 parts of commercial dichlorobenzene and gradually heated, while stir-- ring, to 70 C. to 80 C. together with 30 parts of sulfuryl chloride. After being heated at this temperature for about 6 hours the mass is allowed to cool,.filtered and washed with a small quantity of alcohol. The dichloroben zene which is still adhering to it is then eliminated by means of steam.

The dyestutf forms when-dry a brownlpow- I der and is soluble in sulfuric acid to a winered solution. It dyes cotton from a yellow hydrosulfite vat clear brown tints which iare somewhat redder than those obtainable ac example.

The dyestuff has the ollowing formula:

for about one hour. The dyestufi' which separates is filtered while hot and washed with water until neutral. It is identical with that to Example 1.

. We claim:

1. As new products vat dyestufi's of the folv loWmg composit on following composition:

2. As a new product the vat dyestufl of the following composition:

3 I 2=C 4 Br 1 NH 8/ O=( J2 i 6 1 1 7 N t Br 3. Process of producing vat dyestufl's, which consists in treating the dyestuff of the following. composition with sulfuryl chloride; v

The process of pr oducing vat dyestuffs, which consists in treating the dyestuff of the i L I H s 3 5 'o=2 a I l lg following composition:

with sulfurylchloride in the presence ofan indifferent diluent.

In testimony whereof, we'afiix our signatures.

RICHARD HERZ. FRANZ FARR. KARL THIEss. CARL JOSEF MULLER. 

